CN106479481A - ZnSe/III V race/ZnSexS1 x or ZnSe/III V race/ZnSe/ZnS quantum dot and preparation method thereof - Google Patents
ZnSe/III V race/ZnSexS1 x or ZnSe/III V race/ZnSe/ZnS quantum dot and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of ZnSe/III V race/ZnSexS1‑xOr ZnSe/III V race/ZnSe/ZnS quantum dot and preparation method thereof.This preparation method includes：S1, the first mixed liquor containing ZnSe core and non-coordinating solvent for the preparation；S2, adds group-III element precursor solution to form the second mixed liquor in the first mixed liquor, is warming up to 180～320 DEG C, add V group element precursor solution to be reacted；S3, coats ZnSexS1‑xOr ZnSe/ZnS shell, obtain ZnSe/III V race/ZnSexS1‑xOr ZnSe/III V race/ZnSe/ZnS quantum dot.First in low temperature plus group-III element precursor solution, then high temperature adds V group element precursor solution, it is to avoid the spontaneous nucleation of III V, realizes III V group element shell and perfectly coats on ZnSe core.
Description
Technical field
The present invention relates to technical field of material, in particular to a kind of ZnSe/III-V race/ZnSexS1-xOr
ZnSe/III-V race/ZnSe/ZnS quantum dot and preparation method thereof.
Background technology
At present, by II-VI group elementary composition CdSe quantum dots emission spectrum continuously adjustabe in visible-range, institute
The quantum dot size of preparation is evenly distributed, and the half-peak breadth of spectrum is narrower, after organic-inorganic passivation is carried out to its surface, table
Reveal very high quantum yield and stability, by widely studied and concern.However, employing heavy metal in CdSe quantum dots
, all there is certain toxicity and pollution to human body and natural environment so that it, in application, is limited to by certain in cadmium (Cd),
Therefore synthesis exploitation no cadmium low cadmium quantum dot light emitting material has very major and immediate significance.
Iii-v quantum dot is the focus of no cadmium quantum dot research at present, but the major defect of the type quantum dot is
Efficiency is low, and half-peak is roomy, and stability is poor.At present in document report method, the synthesis of ZnSe/InP/ZnS is no cadmium quantum dot
A developing direction, current green light quantum point can accomplish PL (photoluminescence emission peak) half-peak breadth 50-60nm, quantum efficiency
60% (half-peak breadth is narrower, then peak type is sharper, and color is more purely；The higher the better for quantum efficiency).But also have one from industrial applications
Fixed distance.
Content of the invention
The present invention is intended to provide a kind of ZnSe/III-V race/ZnSexS1-xOr ZnSe/III-V race/ZnSe/ZnS quantum dot
And preparation method thereof, to reduce the PL half-peak breadth of quantum dot, improve luminous quantum efficiency.
To achieve these goals, according to an aspect of the invention, it is provided a kind of ZnSe/III-V race/ZnSexS1-x
Or the preparation method of ZnSe/III-V race/ZnSe/ZnS quantum dot.This preparation method comprises the following steps：S1, preparation contains ZnSe
Core and the first mixed liquor of non-coordinating solvent, the first mixeding liquid temperature≤150 DEG C；S2, adds III unit in the first mixed liquor
Plain precursor solution forms the second mixed liquor, is warming up to 180～320 DEG C, adds V group element precursor solution to be reacted, III unit
Element and V group element are coated on formation iii-v element shell on ZnSe core, and form the quantum dot of race containing ZnSe/III-V the 3rd mixes
Close liquid；S3, coats ZnSexS1-xOr ZnSe/ZnS shell, obtain ZnSe/III-V race/ZnSexS1-xOr ZnSe/III-V race/
ZnSe/ZnS quantum dot, wherein 0≤x≤1.
Further, group-III element is In, and V group element is P or As.
Further, in S2, group-III element precursor solution and the first part is added to be collectively forming the in the first mixed liquor
Two mixed liquors.
Further, in S2, add after V group element precursor solution and Ligands mixing.
Further, the first part is at least one of acids or amine.
Further, Ligands are amine.
Further, in S2, the first mixed liquor adds group-III element precursor solution after being cooled to 25 DEG C～100 DEG C.
Further, in S2, the first mixed liquor adds group-III element precursor solution and the after being cooled to 25 DEG C～100 DEG C
One part.
Further, S3 specifically includes：Add Zn precursor in the 3rd mixed liquor of the quantum dot of race containing ZnSe/III-V, so
Post-heating, to 180～320 DEG C, adds Se and S mixing precursor solution, the ZnSe of synthesisxS1-xIt is coated on iii-v element shell
Surface, obtains ZnSe/III-V race/ZnSexS1-xQuantum dot；Or in the 3rd mixed liquor of the quantum dot of race containing ZnSe/III-V
Add Zn precursor, be then heated to 180～320 DEG C, after being initially charged the reaction completely of Se precursor solution, add S precursor solution anti-
Should, obtain ZnSe/III-V race/ZnSe/ZnS quantum dot.
Further, S1 specifically includes：Zn precursor solution and non-coordinating solvent are mixed and heated to note after 200～350 DEG C
Enter the reaction of Se precursor solution and obtain the first mixed liquor.
Further, Zn precursor solution is fatty acid zinc, selected from zinc acetate, ten sour zinc, Zinc Undecylenate, tetradecylic acid
The solution of one or more of zinc, the group of zinc oleate, hexadecylic acid zinc and zinc stearate composition.
Further, a width of 12-15nm of PL half-peak of ZnSe core.
According to another aspect of the present invention, provide a kind of ZnSe/III-V race/ZnSexS1-xOr ZnSe/III-V race/
ZnSe/ZnS quantum dot.This ZnSe/III-V race/ZnSexS1-xOr ZnSe/III-V race/ZnSe/ZnS quantum dot passes through above-mentioned
A kind of preparation method prepares.
Further, ZnSe/III-V race/ZnSexS1-xOr the half-peak breadth of ZnSe/III-V race/ZnSe/ZnS quantum dot is little
In equal to 45nm, luminous quantum efficiency is more than or equal to 60%.
Application technical scheme, by group-III element precursor solution and V race in the cladding of iii-v element shell
Elemental precursors solution is added separately to, first in (≤150 DEG C) of low temperature plus group-III element precursor solution, then high temperature (220～300
DEG C) plus V group element precursor solution, it is to avoid the spontaneous nucleation of III-V, realize iii-v element shell and perfectly wrap on ZnSe core
Cover, obtain the ZnSe/III-V race quantum dot of half-peak width, then coated.
Brief description
The Figure of description constituting the part of the application is used for providing a further understanding of the present invention, and the present invention shows
Meaning property embodiment and its illustrate for explaining the present invention, does not constitute inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 show embodiment 1 obtained by quantum dot UV and PL spectrum；
Fig. 2 show embodiment 1 obtained by quantum dot transmission electron microscope picture (TEM)；
Fig. 3 show comparative example 1 obtained by quantum dot transmission electron microscope picture (TEM).
Specific embodiment
It should be noted that in the case of not conflicting, the embodiment in the application and the feature in embodiment can phases
Mutually combine.To describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
According to a kind of typical embodiment of the present invention, provide a kind of ZnSe/III-V race/ZnSexS1-xOr ZnSe/III-
The preparation method of V race/ZnSe/ZnS quantum dot.This preparation method comprises the following steps：This preparation method comprises the following steps：
S1, the first mixed liquor containing ZnSe core and non-coordinating solvent for the preparation, the first mixeding liquid temperature≤150 DEG C；S2, to the first mixed liquor
Middle addition group-III element precursor solution forms the second mixed liquor, is warming up to 180～320 DEG C, preferably 220～300 DEG C, adds V race
Elemental precursors solution is reacted, and group-III element and V group element are coated on formation iii-v element shell on ZnSe core, are formed
3rd mixed liquor of the quantum dot of race containing ZnSe/III-V；S3, coats ZnSexS1-xOr ZnSe/ZnS shell, obtain ZnSe/III-V
Race/ZnSexS1-xOr ZnSe/III-V race/ZnSe/ZnS quantum dot, wherein 0≤x≤1.Key to the invention is that iii-v is first
The cladding of plain shell, the high-quality cladding of iii-v element shell combines subsequently suitable ZnS cladding and can obtain narrower PL
Half-peak breadth.In the cladding of iii-v element shell, group-III element precursor solution and V group element precursor solution are added separately to, first
In (≤150 DEG C) of low temperature plus group-III element precursor solution, then (180～320 DEG C) of high temperature plus V group element precursor solution, it is to avoid
The spontaneous nucleation of III-V element, realizes iii-v element shell and perfectly coats on ZnSe core, the narrow ZnSe/ in the peak that is absorbed
Iii-v quantum dot.Wherein, under low temperature, (high temperature with respect to below) adds group-III element, then high temperature injection V group element,
The addition of group-III element and V group element is carried out separately, and such low temperature adds group-III element precursor solution, is conducive to its suction
It is attached to ZnSe surface, high temperature adds the group-III element precursor solution with absorption on ZnSe surface for the V group element precursor solution to react,
Generate and be coated on the InP on ZnSe surface, prevent III and V group element from adding under high temperature simultaneously and spontaneous nucleation (i.e. iii-v unit occurs
Element individually nucleation, rather than grow on ZnSe) and grow uneven.Under high temperature injection V group element can mushroom out and not
It is to produce substantial amounts of spontaneous nucleation.
According to a kind of typical embodiment of the present invention, group-III element is In, and V group element is P or As.Preferably, III
Race's elemental precursors solution is indium salts, selected from the solution of one or more of indium acetate, indium chloride and tetradecylic acid indium.Preferably,
In S2, group-III element precursor solution and the first part is added to be collectively forming the second mixed liquor in the first mixed liquor.Wherein,
One part is at least one of amine or acids, preferably is selected from being made up of tetradecylic acid, ten acid, Oleic acid, eight amine, oleyl amine and trioctylamine
One or more of group.Preferably, V group element precursor solution is selected from three (trimethyl silicon substrate) phosphine (i.e. P (Si (CH3)3), contracting
It is written as TMSP) and/or three (triethyl group silicon substrate) phosphine (i.e. P (Si (CH2CH3)3), be abbreviated as TESP) one or more of molten
Liquid.Preferably, in S2, add after V group element precursor solution and Ligands mixing.Ligands are amine, preferably are selected from eight
One or more of amine, oleyl amine and trioctylamine.The effect of the first part and Ligands is to improve group-III element and unit of V race
Dissolubility in reaction system for the element.
Preferably, in S2, the first mixed liquor adds group-III element precursor solution, S2 step after being cooled to 25 DEG C～100 DEG C
The time of reaction is 5～30min.This response time can determine whether reaction completely according to UV.UV extinction position is permissible
To determine particle size, particle can be with stopped reaction after reaching target sizes, and after preventing ripening, particle monodispersity is deteriorated.S2
In, form the 3rd mixed liquor of described race containing ZnSe/III-V quantum dot after being cooled to 25～150 DEG C of terminating reactions, or do not drop
Warm question response forms the 3rd mixed liquor of described race containing ZnSe/III-V quantum dot completely afterwards；
According to a kind of typical embodiment of the present invention, S3 specifically includes：To the quantum dot of race containing ZnSe/III-V the 3rd
Add Zn precursor in mixed liquor, be then heated to 180～320 DEG C, add Se and S mixing precursor solution, the ZnS of synthesis is coated on
Iii-v element shell layer surface, obtains ZnSe/III-V race/ZnSexS1-xQuantum dot；Or to the quantum of race containing ZnSe/III-V
Add Zn precursor in the 3rd mixed liquor selected, be then heated to 180～320 DEG C, preferably 220～300 DEG C, add Se precursor solution
After reaction completely, form ZnSe/III-V race/ZnSe, then add S precursor solution, react certain time, obtain ZnSe/
Iii-v/ZnSe/ZnS quantum dot.
Preferably, S precursor is selected from sulfur-tributylphosphine, sulfur-tri octyl phosphine, sulfur-octadecylene and hexamethyldisilathiane group
One or more of group becoming.
According to a kind of typical embodiment of the present invention, after Zn precursor and non-coordinating solvent are mixed and heated to 200～350 DEG C
Injection Se precursor solution reaction obtains the first mixed liquor.
Preferably, non-coordinating solvent be selected from hexadecane, one of group of octadecane, hexadecylene and octadecylene composition or
Multiple.
Preferably, Zn precursor is fatty acid zinc, selected from zinc acetate, ten sour zinc, Zinc Undecylenate, tetradecylic acid zinc, Oleic acid
One or more of group of zinc, hexadecylic acid zinc and zinc stearate composition.
Preferably, a width of 12-15nm of PL half-peak of ZnSe core.
According to a kind of typical embodiment of the present invention, ZnSe/III-V race/ZnSexS1-xOr ZnSe/III-V race/
The preparation method of ZnSe/ZnS quantum dot comprises the following steps：S1, prepares ZnSe core：By fatty acid zinc, (fatty acid zinc can first
To be zinc acetate, ten sour zinc, Zinc Undecylenate, tetradecylic acid zinc, zinc oleate, hexadecylic acid zinc, zinc stearate etc.) and octadecylene (1-
Octadecene, ODE) in (200～350 DEG C) dissolvings of high temperature, then (200～350 DEG C) injection Se precursor solutions of high temperature, obtain
The core (particle is homogeneous, launches half-peak width) of high-quality ZnSe, a width of 12-15nm of its PL half-peak；S2, coats InP shell：
After ZnSe nucleation (25 to 150 DEG C) of low temperature add indium salts (indium acetate, indium chloride, tetradecylic acid indium) and part (eight amine, oleyl amine,
Trioctylamine), it is warming up to 180-320 DEG C, when preferably 220-300 DEG C rapid injection P precursor solution (TMSP, TESP) reacts one section
Between, realize the cladding of InP, it is to avoid spontaneous nucleation；This step is committed step, is the principal element affecting follow-up half-peak breadth size；
S3, coats ZnSexS1-xShell：In low temperature, (25～150 DEG C) add a certain amount of zinc precursor (zinc acetate, ten sour zinc, hendecene
Sour zinc, tetradecylic acid zinc, zinc oleate, hexadecylic acid zinc, zinc stearate etc., zinc precursor adds reaction after can also being dissolved in solution),
Aerofluxuss, are warming up to 180-320 DEG C and add a certain proportion of Se and S mixing precursor solution to react certain time, such as, Se precursor is molten
Liquid is selected from selenium-tributylphosphine (Se-TBP), selenium-tri octyl phosphine (Se-TOP), Se- octadecylene solution or suspension (Se-
One or more of ODE), hexamethyl two silicon selenium alkane (Se-TMS)).S precursor solution selects sulfur-tributylphosphine (S-TBP),
One or more of sulfur-tri octyl phosphine (S-TOP), sulfur-octadecylene (S-ODE), hexamethyldisilathiane (S-TMS)).Or bag
Cover ZnSe/ZnS shell：In low temperature, (25～150 DEG C) add a certain amount of zinc precursor solution (zinc acetate, ten sour zinc, undecylenic acid
Zinc, tetradecylic acid zinc, zinc oleate, hexadecylic acid zinc, zinc stearate etc.), aerofluxuss, before being warming up to 180-320 DEG C of a certain amount of Se of addition
Liquid solution reacts certain time, and Se precursor solution is selected from selenium-tributylphosphine (Se-TBP), selenium-tri octyl phosphine (Se-TOP), Se-
One or more of octadecylene solution or suspension (Se-ODE), hexamethyl two silicon selenium alkane (Se-TMS)).It is subsequently adding one
After quantitative S precursor solution reaction completely, S precursor solution is selected from sulfur-tributylphosphine (S-TBP), sulfur-tri octyl phosphine (S-TOP),
One or more of sulfur-octadecylene (S-ODE), hexamethyldisilathiane (S-TMS)).
According to a kind of typical embodiment of the present invention, provide a kind of ZnSe/III-V race/ZnSexS1-xOr ZnSe/III-
V race/ZnSe/ZnS quantum dot.This ZnSe/III-V race/ZnSexS1-xOr ZnSe/III-V race/ZnSe/ZnS quantum dot is by upper
State any one preparation method to prepare.ZnSe/III-V race/ZnSexS1-xOr ZnSe/III-V race/ZnSe/ZnS quantum dot
Half-peak breadth is less than or equal to 45nm, and luminous quantum efficiency is more than or equal to 60%.
Further illustrate beneficial effects of the present invention below in conjunction with embodiment.There is no clear and definite step in the present invention,
Can be realized by ordinary skill in the art means.
Embodiment 1
Weigh 0.2mmol zinc stearate and 6g ODE in three-necked bottle, aerofluxuss 10min in noble gases, it is warming up to 250 DEG C
Injection 0.1mmol Se-ODE solution, reaction 20min obtains ZnSe core；
It is cooled to 100 DEG C plus 0.1mmol In (Ac)3Solid, is warming up to TMSP and 0.1ml of 270 DEG C of injection 0.1mmol
Oleyl amine, reacts 10min；
It is cooled to 100 DEG C plus 0.5mmol zinc stearate, aerofluxuss 10min, is warming up to 270 DEG C, inject Se containing 0.06mmol
TBP solution with 0.24mmol S；It is cooled to 100 DEG C.
Embodiment 2
Weigh 0.2mmol zinc stearate and 6g ODE in three-necked bottle, aerofluxuss 10min in noble gases, it is warming up to 300 DEG C
Injection 0.1mmol Se-ODE solution, reaction 20min obtains ZnSe core；
It is cooled to 25 DEG C plus 0.1mmol In (Ac)3Solid, is warming up to TMSP the and 0.1ml oil of 220 DEG C of injection 0.1mmol
Amine, reacts 5min；
It is cooled to 25 DEG C plus 0.5mmol zinc stearate, aerofluxuss 10min, be warming up to 270 DEG C, the Se-TBP of injection 0.3mmol
Solution, is cooled to 25 DEG C.
Embodiment 3
Weigh 0.2mmol zinc stearate and 6g ODE in three-necked bottle, aerofluxuss 10min in noble gases, it is warming up to 350 DEG C
Injection 0.1mmol Se-ODE solution, reaction 20min obtains ZnSe core；
It is cooled to 150 DEG C plus 0.1mmol In (Ac)3Solid, is warming up to TMSP and 0.1ml of 300 DEG C of injection 0.1mmol
Oleyl amine, reacts 30min；
It is cooled to 150 DEG C plus 0.5mmol zinc stearate, aerofluxuss 10min, be warming up to 270 DEG C, the S-TBP of injection 0.3mmol
Solution, is cooled to 150 DEG C.
Embodiment 4
Weigh 0.2mmol zinc acetate and 6g ODE in three-necked bottle, aerofluxuss 10min in noble gases, it is warming up to 300 DEG C of notes
Enter 0.1mmol Se-ODE solution, reaction 20min obtains ZnSe core；
It is cooled to 150 DEG C plus 0.1mmol indium chloride solid, be warming up to TMSP and 0.1ml eight of 180 DEG C of injection 0.1mmol
Amine, reacts 10min；
It is cooled to 150 DEG C plus 0.5mmol zinc stearate, aerofluxuss 10min, is warming up to 270 DEG C, inject Se containing 0.15mmol
With the TBP solution of 0.15mmol S, it is cooled to 150 DEG C.
Embodiment 5
Weigh 0.2mmol zinc acetate and 6g ODE in three-necked bottle, aerofluxuss 10min in noble gases, it is warming up to 300 DEG C of notes
Enter 0.1mmol Se-ODE solution, reaction 20min obtains ZnSe core；
It is cooled to 120 DEG C plus 0.1mmol indium acetate solid, be warming up to TMSP the and 0.1ml oil of 300 DEG C of injection 0.1mmol
Amine, reacts 10min；
It is cooled to 150 DEG C plus 0.5mmol zinc stearate, aerofluxuss 10min, be warming up to 270 DEG C, the Se- of injection 0.15mmol
TBP solution, reacts 10min, is then injected into the S-TBP solution of 0.15mmol, reacts 20min, is cooled to 150 DEG C.
Embodiment 6
Weigh 0.2mmol zinc acetate and 6g ODE in three-necked bottle, aerofluxuss 10min in noble gases, it is warming up to 300 DEG C of notes
Enter 0.1mmol Se-ODE solution, reaction 20min obtains ZnSe core；
It is cooled to 150 DEG C plus 0.1mmol indium chloride solid, be warming up to TMSAs and 0.1ml eight of 180 DEG C of injection 0.1mmol
Amine, reacts 10min；
It is cooled to 150 DEG C plus 0.5mmol zinc stearate, aerofluxuss 10min, is warming up to 270 DEG C, inject Se containing 0.15mmol
With the TBP solution of 0.15mmol S, it is cooled to 150 DEG C.
Embodiment 7
Weigh 0.2mmol zinc stearate and 6g ODE in three-necked bottle, aerofluxuss 10min in noble gases, it is warming up to 250 DEG C
Injection 0.1mmol Se-ODE solution, reaction 20min obtains ZnSe core；
It is cooled to 100 DEG C plus 0.1mmol In (Ac)3Solid, is warming up to the TMSP of 270 DEG C of injection 0.1mmol, reaction
10min；
It is cooled to 100 DEG C plus 0.5mmol zinc stearate, aerofluxuss 10min, is warming up to 270 DEG C, inject Se containing 0.06mmol
TBP solution with 0.24mmolS；It is cooled to 100 DEG C.
Embodiment 8
Weigh 0.2mmol zinc stearate and 6g ODE in three-necked bottle, aerofluxuss 10min in noble gases, it is warming up to 250 DEG C
Injection 0.1mmol Se-ODE solution, reaction 20min obtains ZnSe core；
It is cooled to 100 DEG C plus 0.1mmol In (Ac)3Solid, is warming up to TMSP and 0.1ml of 320 DEG C of injection 0.1mmol
Oleyl amine, reacts 10min；
It is cooled to 100 DEG C plus 0.5mmol zinc stearate, aerofluxuss 10min, is warming up to 270 DEG C, inject Se containing 0.06mmol
TBP solution with 0.24mmol S；It is cooled to 100 DEG C.
Embodiment 9
Weigh 0.2mmol zinc stearate and 6g ODE in three-necked bottle, aerofluxuss 10min in noble gases, it is warming up to 250 DEG C
Injection 0.1mmol Se-ODE solution, reaction 20min obtains ZnSe core；
It is cooled to 100 DEG C plus 0.1mmol In (Ac)3Solid and 0.05ml Oleic acid, are warming up to 270 DEG C of injection 0.1mmol's
TMSP, reacts 10min；
It is cooled to 100 DEG C plus 0.5mmol zinc stearate, aerofluxuss 10min, is warming up to 270 DEG C, inject Se containing 0.06mmol
TBP solution with 0.24mmolS；It is cooled to 100 DEG C.
Embodiment 10
Weigh 0.2mmol zinc stearate and 6g ODE in three-necked bottle, aerofluxuss 10min in noble gases, it is warming up to 250 DEG C
Injection 0.1mmol Se-ODE solution, reaction 20min obtains ZnSe core；
It is cooled to 100 DEG C plus 0.1mmol In (Ac)3Solid and 0.1ml Oleic acid and 0.05ml lauryl amine, are warming up to 270 DEG C
The TMSP of injection 0.1mmol, reacts 10min；
It is cooled to 100 DEG C plus 0.5mmol zinc stearate, aerofluxuss 10min, is warming up to 270 DEG C, inject Se containing 0.06mmol
TBP solution with 0.24mmolS；It is cooled to 100 DEG C.
Embodiment 11
Weigh 0.2mmol zinc stearate and 6g ODE in three-necked bottle, aerofluxuss 10min in noble gases, it is warming up to 250 DEG C
Injection 0.1mmol Se-ODE solution, reaction 20min obtains ZnSe core；
It is cooled to 100 DEG C plus 0.1mmol In (Ac)3Solid and 0.05ml lauryl amine, are warming up to 270 DEG C of injection 0.1mmol
TMSP, react 10min；
It is cooled to 100 DEG C plus 0.5mmol zinc stearate, aerofluxuss 10min, is warming up to 270 DEG C, inject Se containing 0.06mmol
TBP solution with 0.24mmolS；It is cooled to 100 DEG C.
Comparative example 1
S1, weighs 0.2mmol zinc stearate and 6g ODE in three-necked bottle, and aerofluxuss 10min is warming up to 300 DEG C of injections
0.1mmol Se-ODE solution, reaction 20min obtains ZnSe core；
S2, is cooled to the TMSP, Ran Housheng of 100 DEG C plus 0.1mmol In (Ac) 3 solid and 0.1ml oleyl amine and 0.1mmol
Temperature, to 270 DEG C, reacts 10min；
S3, is cooled to 100 DEG C plus 0.5mmol zinc stearate, aerofluxuss 10min, is warming up to 270 DEG C, and injection contains 0.06mmol
The TBP solution of Se and 0.24mmol S；It is cooled to 100 DEG C.
Comparative example 2
S1, weighs 0.2mmol zinc stearate and 6g ODE in three-necked bottle, and aerofluxuss 10min is warming up to 300 DEG C of injections
0.1mmol Se-ODE solution, reaction 20min obtains ZnSe core；
S2, is cooled to the TMSAs, Ran Housheng of 100 DEG C plus 0.1mmol In (Ac) 3 solid and 0.1ml oleyl amine and 0.1mmol
Temperature, to 270 DEG C, reacts 10min；
S3, is cooled to 150 DEG C plus 0.5mmol zinc stearate, aerofluxuss 10min, is warming up to 270 DEG C, and injection contains 0.15mmol
The TBP solution of Se and 0.15mmol S, is cooled to 150 DEG C.
Comparative example 3
Weigh 0.2mmol zinc acetate and 6g ODE in three-necked bottle, aerofluxuss 10min in noble gases, it is warming up to 300 DEG C of notes
Enter 0.1mmol Se-ODE solution, reaction 20min obtains ZnSe core；
It is cooled to the TMSP of 120 DEG C plus 0.1mmol indium acetate solid and 0.1ml eight amine and 0.1mmol, be warming up to 300 DEG C
Reaction 10min；
It is cooled to 150 DEG C plus 0.5mmol zinc stearate, aerofluxuss 10min, be warming up to 270 DEG C, the Se- of injection 0.15mmol
TBP solution, reacts 10min, is then injected into the S-TBP solution of 0.15mmol, reacts 20min, is cooled to 150 DEG C.
The quantum dot methanol purification that above example and comparative example obtain, is then peeled off purification with acetone precipitation, finally
It is dissolved in toluene and carries out UV (ultra-violet absorption spectrum) and the sign of PL (emission spectrum), using fluorescence spectrophotometer test half-peak breadth and can
See light emitting peak, ultraviolet absorption peak is detected using ultraviolet-visual spectrometer, with integrating sphere measurement quantum dot light emitting efficiency, data is shown in
Table 1.
Table 1
Can be seen that the product preparing using technical scheme from the data of table 1, quantum efficiency obtains
Very big raising.
Fig. 1 is UV the and PL spectrogram obtaining quantum dot of embodiment 1, can draw the suction of last gained quantum dot from figure
Receiving peak position is 486nm, and emission peak positions are 518nm, launch a width of 42nm of half-peak.
Fig. 2 is the transmission electron microscope picture obtaining quantum dot of embodiment 1, it can be seen that gained quantum dot granule divides
Cloth is homogeneous, is spherical, illustrates that the method for embodiment 1 is conducive to the growth of quantum dot.
Fig. 3 is the transmission electron microscope picture obtaining quantum dot of comparative example 1, it can be seen that quantum dot pattern heterogeneity,
Illustrate that the method is unfavorable for the cladding of shell.
To sum up, in the cladding of iii-v element shell, group-III element precursor solution and V group element precursor solution are separated
Add, first in (≤150 DEG C) of low temperature plus group-III element precursor solution, then (180～320 DEG C) of high temperature plus V group element precursor are molten
Liquid, it is to avoid the spontaneous nucleation of III-V, realizes iii-v element shell and perfectly coats on ZnSe core, the peak that is absorbed is narrow
ZnSe/III-V race quantum dot.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (14)
1. a kind of ZnSe/III-V race/ZnSexS1-xOr the preparation method of ZnSe/III-V race/ZnSe/ZnS quantum dot, its feature
It is, comprise the following steps：
S1, the first mixed liquor containing ZnSe core and non-coordinating solvent for the preparation, described first mixeding liquid temperature≤150 DEG C；
S2, adds group-III element precursor solution to form the second mixed liquor in described first mixed liquor, is warming up to 180～320
DEG C, add V group element precursor solution to be reacted, described group-III element and described V group element are coated on shape on described ZnSe core
Become iii-v element shell, form the 3rd mixed liquor of the quantum dot of race containing ZnSe/III-V；
S3, coats ZnSexS1-xOr ZnSe/ZnS shell, obtain described ZnSe/III-V race/ZnSexS1-xOr ZnSe/III-V race/
ZnSe/ZnS quantum dot, wherein 0≤x≤1.
2. it is characterised in that described group-III element is In, described V group element is P to preparation method according to claim 1
Or As.
3. preparation method according to claim 1 is it is characterised in that in described S2, add in described first mixed liquor
Described group-III element precursor solution and the first part are collectively forming the second mixed liquor.
4. preparation method according to claim 1 is it is characterised in that in described S2, described V group element precursor solution and
Add after two part mixing.
5. preparation method according to claim 3 is it is characterised in that described first part is at least the one of acids or amine
Kind.
6. preparation method according to claim 4 is it is characterised in that described Ligands are amine.
7. preparation method according to claim 1 is it is characterised in that in described S2, described first mixed liquor is cooled to 25
DEG C～100 DEG C after add described group-III element precursor solution.
8. preparation method according to claim 3 is it is characterised in that in described S2, described first mixed liquor is cooled to 25
DEG C～100 DEG C after add described group-III element precursor solution and described first part.
9. preparation method according to claim 1 is it is characterised in that described S3 specifically includes：To described containing ZnSe/III-
Add Zn precursor in 3rd mixed liquor of V race quantum dot, be then heated to 180～320 DEG C, add Se and S mixing precursor solution,
The ZnSe of synthesisxS1-xIt is coated on described iii-v element shell layer surface, obtain described ZnSe/III-V race/ZnSexS1-xQuantum
Point；Or add Zn precursor in the 3rd mixed liquor of described race containing ZnSe/III-V quantum dot, be then heated to 180～320
DEG C, after being initially charged the reaction completely of Se precursor solution, add the reaction of S precursor solution, obtain described ZnSe/III-V race/ZnSe/
ZnS quantum dot.
10. preparation method according to claim 1 is it is characterised in that described S1 specifically includes：By Zn precursor solution and institute
State injection Se precursor solution reaction after non-coordinating solvent is mixed and heated to 200～350 DEG C and obtain described first mixed liquor.
11. preparation methoies according to claim 9 or 10, it is characterised in that described Zn precursor solution is fatty acid zinc, are selected
In free zinc acetate, ten sour zinc, Zinc Undecylenate, tetradecylic acid zinc, the group of zinc oleate, hexadecylic acid zinc and zinc stearate composition one
Plant or multiple solution.
12. preparation methoies according to claim 1 are it is characterised in that a width of 12-15nm of PL half-peak of described ZnSe core.
A kind of 13. ZnSe/III-V race/ZnSexS1-xOr ZnSe/III-V race/ZnSe/ZnS quantum dot is it is characterised in that described
ZnSe/III-V race/ZnSexS1-xOr ZnSe/III-V race/ZnSe/ZnS quantum dot passes through as any one of claim 1 to 12
Described preparation method prepares.
14. ZnSe/III-V race/ZnSe according to claim 13xS1-xOr ZnSe/III-V race/ZnSe/ZnS quantum dot,
It is characterized in that, described ZnSe/III-V race/ZnSexS1-xOr the half-peak breadth of ZnSe/III-V race/ZnSe/ZnS quantum dot is less than
Equal to 45nm, luminous quantum efficiency is more than or equal to 60%.
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